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- 1 - The effectiveness of conventional trickling filter treatment plants at reducing concentrations of copper in wastewaters. Dominik Ziolko a , David Hala a , John N. Lester b and Mark D. Scrimshaw a,* a Institute for the Environment, Brunel University, Uxbridge, Middlesex, UB83 PH, UK b School of Applied Science, Centre for Water Science, Cranfield University, Bedfordshire, MK43 0AL, UK * Corresponding author. Tel.: +44 (0)1895 267 299. E-mail: [email protected]. Abstract Eight different sewage treatment works were sampled in the North West of England. The effectiveness of the conventional treatment processes (primary sedimentation and biological trickling filters) as well as various tertiary treatment units in terms of both total and dissolved copper removal was evaluated. The removal of total copper across primary sedimentation averaged 53% and were relatively consistent at all sites, however, at three sites the removal of dissolved copper also occurred at this stage of treatment. Removal of total copper by the biological trickling filters averaged 49%, however, substantial dissolution of copper occurred at two sites, which highlighted the unpredictability of this treatment process in the removal of dissolved copper. Copper removal during tertiary treatment varied considerable even for the same treatment processes installed at different sites, primarily due to the variability of insoluble copper removal, with little effect on copper in the dissolved form being observed. The proportion of dissolved copper increased significantly during treatment, from an average of 22% in crude sewages to 55% in the final effluents. There may be the potential to optimise existing, conventional treatment processes (primary or biological treatment) to enhance dissolved copper removal, possibly reducing the requirement for installing any tertiary processes specifically for the removal of copper. Keywords: copper; sewage; removal efficiency; mass balance; primary treatment; trickling filters

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- 1 -

The effectiveness of conventional trickling filter treatment plants at

reducing concentrations of copper in wastewaters.

Dominik Ziolkoa, David Hala

a, John N. Lester

b and Mark D. Scrimshaw

a,*

a Institute for the Environment, Brunel University, Uxbridge, Middlesex, UB83 PH, UK

b School of Applied Science, Centre for Water Science, Cranfield University, Bedfordshire,

MK43 0AL, UK

* Corresponding author. Tel.: +44 (0)1895 267 299. E-mail: [email protected].

Abstract

Eight different sewage treatment works were sampled in the North West of England.

The effectiveness of the conventional treatment processes (primary sedimentation and

biological trickling filters) as well as various tertiary treatment units in terms of both

total and dissolved copper removal was evaluated. The removal of total copper across

primary sedimentation averaged 53% and were relatively consistent at all sites,

however, at three sites the removal of dissolved copper also occurred at this stage of

treatment. Removal of total copper by the biological trickling filters averaged 49%,

however, substantial dissolution of copper occurred at two sites, which highlighted the

unpredictability of this treatment process in the removal of dissolved copper. Copper

removal during tertiary treatment varied considerable even for the same treatment

processes installed at different sites, primarily due to the variability of insoluble

copper removal, with little effect on copper in the dissolved form being observed. The

proportion of dissolved copper increased significantly during treatment, from an

average of 22% in crude sewages to 55% in the final effluents. There may be the

potential to optimise existing, conventional treatment processes (primary or biological

treatment) to enhance dissolved copper removal, possibly reducing the requirement

for installing any tertiary processes specifically for the removal of copper.

Keywords: copper; sewage; removal efficiency; mass balance; primary treatment;

trickling filters

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1. Introduction

Copper is one of the metals that are of particular concern in relation to water

quality, because although an essential element, elevated concentrations in the aquatic

environment may result in toxicological effects (de Oliveira-Filho et al., 2004; de

Schamphelaere et al., 2004). Copper has been classified under the Water Framework

Directive as a potential main pollutant (Annex VIII) for which an environmental

quality standard (EQS), if required, should be established at the national level

(European Commission, 2000). At present, in England and Wales for water bodies

achieving good ecological status, the freshwater EQS for copper ranges from 1-28

μg/l (dissolved copper annual average) depending on water hardness, falling to 5 μg/l

in coastal and estuarine areas (UKTAG, 2008). Discharge consents for sewage

treatment works (STW) however, are set based on the total copper concentrations

(particulate plus dissolved copper). Removal of both particulate and dissolved copper

fractions during sewage treatment is therefore relevant to achieve compliance with

increasingly stringent consents and EQS and achieving this with existing unit

treatment processes may be challenging (Ziolko et al., in press).

In developed countries concentrations of copper in sewage have generally

decreased in comparison to the late 1970s (Ziolko et al., in press). However,

contemporary concentrations remain significant when compared with EQS and

consents, especially for receiving waters that are soft in nature and offer limited

natural dilution for final effluents. Thus STW, although not designed to do so, are

expected to reduce the load of copper discharged to the aquatic environment.

However, most contemporary data available on copper concentrations in sewage

(Sorme and Lingerkvist, 2002; Karvelas et al., 2003; Buzier et al., 2006; Rule et al.,

2006; Oliveira et al., 2007) focus on total metal, leaving a paucity of information on

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the dissolved fraction, despite phase distribution being recognised as a significant

factor in determining the mechanism and extent of copper removal in STW (Kempton

et al., 1983; Rudd et al., 1983a; Lawson et al., 1984a; Kempton et al., 1987a, b).

There are effectively two treatment stages in conventional sewage treatment,

primary sedimentation and biological treatment, where copper (Lester et al., 1979),

and other elements (Stoveland et al., 1979a) may be removed. During primary

treatment, removal is physical, and depends upon the presence of metal in an

insoluble and settleable form (Kempton et al., 1987a, b). Two factors that have the

biggest impact on metal removal at this stage are therefore copper partitioning

between the particulate and dissolved phases in crude sewage and the efficiency of

suspended solids removal (Lawson et al., 1984b, c, d; Kempton et al., 1987a).

Typically no removal of dissolved copper is reported at this stage of treatment and as

a result the proportion of dissolved to particulate copper in the settled sewage

increases (Olivier and Cosgrove, 1974; Stoveland and Lester, 1980; Santarsiero et al.,

1998; Karvelas et al., 2003).

Secondary biological treatment is predominantly based on one of two

processes, a biological reactor consisting of either suspended growth (activated

sludge) or an attached growth process (trickling filters) each followed by a phase

separator (secondary sedimentation). In the activated sludge process the majority of

the biomass removed in the secondary sedimentation tank is recycled to the aerator as

returned activated sludge (RAS) a defining characteristic of the process (Metcalf and

Eddy, 2004). Biological treatment processes are theoretically capable of removing

both dissolved copper, mostly through sorption to the extracellular polymeric

substances (EPS) produced by bacteria, as well as copper associated with solids,

through settling with sludge flocs (Brown and Lester, 1979; Rudd et al., 1983b; Liu et

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al., 2001). However, due to the strong affinity of copper for dissolved organic ligands

and/or possibility of release of EPS from the bacterial cell capsules, an increase in

dissolved metal is also possible (Stoveland et al., 1979b; Rudd et al., 1988; Landner

and Reuther, 2004; Ziolko et al., in press). The mechanism of copper removal in

trickling filters is believed to be not dissimilar to that occurring in the activated sludge

process (Lester, 1987) however, although trickling filters are extensively used in the

UK, with over 800 STWs utilising them as a biological treatment stage in the South-

East region alone (Koh et al., 2008), they have not previously been studied in terms of

copper removal and therefore the exact mechanism of removal remains to be

established.

The biological treatment stage is increasingly followed by a range of different

types of tertiary treatment used to reduce biochemical oxygen demand, suspended

solids and ammonia concentration in effluents. Such treatment may possibly assist in

further reduction of copper concentrations in final effluents, however, these processes

were not specifically designed to remove copper, and their effectiveness is not well

documented (Kobler and Boller, 1997; Hamoda et al., 2004).

The aim of this study was to determine the concentrations of both total and

dissolved copper in the sewage at the different stages of sewage treatment at a number

of STWs in the North West of England in order to evaluate the effectiveness of

various unit treatment processes in removing copper.

2. Methodology

2.1. Description of STWs and sampling strategy

Eight STWs were sampled between November 2006 and November 2007.

Biological treatment at seven sites consisted of trickling filters (these locations are

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identified as TF1 to TF7), and one site utilised an activated sludge plant, identified as

ASP. The sampling dates, site characteristics and their operational parameters, such as

proportion of returned liquors and recirculation over trickling filters, together with

details of any tertiary treatment processes utilised at each STW are presented in Table

1. All catchments were predominantly domestic with less than 11% of the total copper

load to the STWs from named traders, with the exception of TF3 where trade input

was estimated to be 20% of total load in crude sewage (Pers. Comm. United Utilities).

Samples of the influent and effluent from each unit treatment process were

taken every four hours from 10:00 on Monday through to 10:00 on Friday. Further

sampling points were added where samples could beneficially be taken, such as

combined flows of crude sewage with returned liquors or settled sewage with

recirculated flows (Figs. S1-S8 in supplementary material). Samples of sludges and

returned liquors, such as co-settled sludge from primary sedimentation, humus sludge

(from secondary sedimentation following biological treatment), decant liquors from

sludge treatment or backwashes from tertiary treatment processes were collected

daily, or as dictated by operation at each site.

Table 1 Site characteristics and operational parameters recorded during the

sampling periods.

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2.2. Sample preparation

For the analysis of the concentrations of total copper in the influents and

effluents, 40 ml samples were acidified with 2 ml of 70% Optima-grade nitric acid

(Seastar Chemicals Inc., Pittsburgh, PA, USA) and then transferred to digestion

vessels for microwave assisted acid digestion undertaken on-site according to EPA

Method 3015, utilising a CEM Mars 5 digester with XP-1500 Plus vessels (CEM,

Matthews, NC, USA). For sludge and returned liquors samples containing suspended

solids concentrations greater than 1000 mg/l, prior to digestion (EPA Method 3051)

samples were adjusted to 0.1 g/l of solids by dilution with Ultrapure water (Millipore

UK, Watford, UK), and further acidified by addition of 1 ml of Optima-grade nitric

acid.

Analysis for dissolved copper involved filtration of the sample through a 0.45

μm cellulose nitrate membrane filter (VWR International, Darmstadt, Germany)

combined with a glass micro-fibre GF/D pre-filter (Whatman, Maidstone, UK). Prior

to filtration of the bulk sample, filters were washed with approximately 5 ml of

sample, which was discarded. The filtrate (40 ml) was then acidified with 1 ml of

Optima-grade nitric acid in order to solubilise copper prior to quantification. For

sludge and returned liquors samples with high solids content, samples were

centrifuged at 5000g for 30 minutes prior to filtration.

All glassware and digestion vessels used during the work were subject to a 2-

stage cleaning procedure using 3% solution of Decon90 (Decon Laboratories,

Brighton, UK) and 3% solution of nitric acid (Merck, Darmstadt, Germany) and

rinsed with Ultrapure water after each step.

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2.3. Quantification of copper

Copper analyses were performed with a model 4110 ZL Zeeman-corrected

graphite furnace atomic absorption spectrometer (Perkin-Elmer, Beaconsfield, UK)

using a copper hollow cathode lamp (324.8 nm wavelength, 15 mA) and AS-72

autosampler with 2 ml polyethylene disposable sample cups. Calibration was

undertaken using 1, 2, 5, 10, 20 and 50 µg/l freshly prepared copper standards. Prior

to analysis, where necessary, samples were diluted so as to allow for the detection of

copper in the linear range of the calibration curve (Sterritt and Lester, 1980).

Five batches of unspiked samples together with samples spiked at low and

high standard additions were analysed for both total and dissolved copper to

characterise the method performance. Samples for both total (unfiltered and digested)

and dissolved copper (filtered, but not digested) spiked at low and high additions

exhibited no significant differences between batches with an overall recovery of

100% for total and 90% for dissolved copper. Recoveries for dissolved copper may be

explained by matrix effects in undigested samples (Belarra et al., 2000). All reported

results were corrected for these recoveries.

2.4. Data analysis

Statistical analyses were performed with JMP® 7 (SAS Institute, Cary, NC,

USA). Variance in the measured concentration of dissolved copper in samples from

the inlet and outlet of the unit treatment processes was analysed using the ANOVA

test. The post-hoc Tukey’s test was than used to determine where a statistically

significant difference existed between mean concentrations before and after a

treatment process.

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2.5. Mass balance calculations

The mean daily flux of total copper through the unit treatment processes at

each site was calculated using concentrations and flows from data collected over the

sampling period. Changes in the flows resulting from the addition of returned liquors,

recirculation over trickling filters or due to desludging and backwashing were taken

into account. Data for fluxes through the works in many cases were calculated by

summation of measured values where flows combined, or subtraction where flow

streams split and these values are enclosed in boxes when presented in the mass

balance diagrams. Due to the uncertainty regarding the exact volumes of sludges and

returns and wide variability in their solid content, daily copper fluxes through the

works were not calculated.

3. Results

3.1. Spatial and temporal variation in copper concentrations in the crude sewage

The average weekly concentrations of total and dissolved copper determined

in the crude sewage at the eight sites are presented in Fig. 1. At the ASP it was not

possible to obtain crude sewage prior to the addition of returned liquors and therefore

the total copper concentration in the crude sewage was calculated using the mass

balance approach described above, with no attempt made to estimate dissolved copper

concentrations due to uncertainty regarding partitioning. There was some evidence of

spatial variation in both total (14.8 µg/l at TF1 to 107 µg/l at TF4) and dissolved (3.0

µg/l at TF2 to 7.7 µg/l at TF4) copper concentrations. Copper in the dissolved phase

accounted for between 7% (TF4) to 30% (TF3) of the total metal in the crude sewage,

which demonstrates that not only the total concentrations of copper entering the

STWs, but also the distribution between particulate and dissolved phases may vary

considerably.

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Fig. 1. Total (■) and dissolved (□) copper concentrations (µg/l) in crude sewage.

It was also apparent that there was temporal variation in the concentrations of

both total and dissolved copper in the crude sewage entering each of the treatment

works. A typical example of the dynamic nature of the crude sewage, which also

demonstrates the link between diurnal flow patterns and copper concentrations in dry

weather, is shown in Fig. 2. The distinct diurnal pattern can be distinguished with the

lowest concentrations of copper consistently observed at the 06:00 sampling point.

Even during wet weather, which occurred most frequently at TF3, with FTFT

throughout the week averaging 92% of the design capacity (Table 1), a diurnal flow

pattern remained evident. The increase in copper concentrations with the increasing

flow rate during the day time implied the presence of a copper source with

concentrations above those present in runoff. As estimated inputs from trade were

mininal, the implication is that this source was of domestic origin.

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Fig. 2. - Temporal variation in total (■) and dissolved (□) copper concentrations (µg/l)

showing a diurnal pattern with flow (l/s) to full treatment (―) at TF5.

3.2. The flux of copper through the sewage treatment works

At all sites, before crude sewage entered the primary sedimentation tanks it

was combined with the returned liquors streams. The concentrations of copper present

in some of the returned liquors (Table 2) were up to two orders of magnitude above

those observed in crude sewage (Fig. 1), indicating the potential impact that returns

may have on the load to primary treatment. Concentrations of total copper varied

considerably, not only between different return streams, but also at different sites for

the same return, however, in all cases copper was predominantly associated with the

solid phase.

Obtaining representative samples for flows of combined crude sewage plus

returned liquors was, however, difficult as returned liquor flows were frequently

unpredictable and access to suitable sampling points restricted. Fluxes to the primary

sedimentation tanks were therefore calculated using appropriate data on

concentrations and flows or volumes and compared to measured values (where

0.0

5.0

10.0

15.0

20.0

25.0

30.0

35.0

40.0

Mondy 1

0:00

Mondy 1

4:00

Mondy 1

8:00

Mondy 2

2:00

Tuesday

02:00

Tuesday

06:00

Tuesday

10:00

Tuesday

14:00

Tuesday

18:00

Tuesday

22:00

Wed

nesday

02:0

0

Wed

nesday

06:0

0

Wed

nesday

10:0

0

Wed

nesday

14:0

0

Wed

nesday

18:0

0

Wed

nesday

22:0

0

Thursd

ay 02

:00

Thursd

ay 06

:00

Thursd

ay 10

:00

Thursd

ay 14

:00

Thursd

ay 18

:00

Thursd

ay 22

:00

Friday

02:00

Friday

06:00

Friday

10:00

Cop

per

Con

cent

ratio

n, µ

g/l .

0

50

100

150

200

Flow

, l/s

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available) for calculating and validating the mass balances for each site, which are

available in the supplementary information (Figs. S1-S8). These figures present the

flux of total copper in kg/day through the works, with values determined from

measured concentrations in open text, and calculated values, from combing two or

more flow streams, presented in text boxes. This approach was reliable for

quantifying the flux of total metal, however, this method is unsuitable for quantifying

the flux of copper present in the dissolved phase due to uncertainty related to

partitioning when two or more flows combine.

Although the volume of returned liquors did not account for a large proportion

of flow to the STWs, on average 8% (Table 1), their impact on the flux of copper to

the primary sedimentation tanks was significant. Copper in the returns accounted for

27% (the ASP) to 66% (TF3) of the load of total metal to the primary sedimentation

tanks with the major component typically being associated with biological solids,

either humus returns or surplus activated sludge. At a number of sites, where

representative samples of crude sewage plus returned liquors were obtained (e.g. TF3,

TF4 and TF7), fluxes to primary sedimentation tanks which were based on measured

concentrations at this same point, compared favourably with the calculated loads

(Figs. S2, S4, S7). However, at TF1 and TF6 (Figs. S1, S6), it was apparent that

sampling did not “catch” the total load present in the combined crude sewage and

returned liquors, indicating the importance of calculating the load of the total copper

by combining the flux in crude sewage and returned liquors.

3.3. The effectiveness of unit treatment processes at removing copper

The average removal of total copper based on fluxes through the STW

(including the impact of relevant returns) and dissolved copper (based on measured

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concentrations) during conventional primary and biological treatment are summarised

in Table 3. The removal efficiencies for total copper have been calculated based on

values obtained from fluxes through the STW and therefore they include copper in

returned liquors and recirculation flows (where relevant), whereas values for the

dissolved metal fraction are determined from measured concentrations which as

explained, may not have captured internal return flows within each STW. However, it

is known that concentrations of dissolved copper in the returns were relatively low

(Table 2) and may not have any significant impact.

Table 2 Mean weekly total and dissolved copper concentrations (µg/l) in return

flows.

Site Humus Return Decant Liquor Backwash

Total Diss. Total Diss. Total Diss.

TF1 2144 0.5 - - - -

TF2 6676 1.8 111 0.8 50 2.9

TF3 1854 1.5 1274 0.4 63 4.1

TF4 4689 3.9 809 1.2 663 3.7

TF5 375 4.0 249 1.1 - -

TF6 380 2.8 1616 2.6 34.5 4.3

TF7 48 2.6 129 2.2 - -

ASP 837a 1.7

a - - - -

a Surplus activated sludge

The removal of total copper across the primary sedimentation tanks was

generally consistent at all sites, ranging from 49% (TF4) to 60% (TF2), with the

exception of TF6, where removal averaged just 38% over the sampling period. In

addition to the removal of copper associated with solids, removal of dissolved copper

was also observed at TF1, TF3, TF5 and TF7, with efficiencies reaching up to 49%

(TF7). However, at the other sites, there was no difference between crude and settled

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sewage concentrations. The variability in the removal of dissolved copper was

possibly influenced by both variations in the proportion of returned liquors added to

the crude sewage prior to primary sedimentation (Table 1) as well as differences in

the nature of the returned liquors, such as redox potential or suspended solids

concentration, which may have influenced subsequent partitioning during primary

sedimentation.

During biological treatment, at the majority of the sites utilising trickling

filters removal of total copper was fairly consistent (Table 3), ranging from 44%

(TF7) to 55% (TF5), although, the potential for variability was highlighted by two

sites exhibiting more extreme removals of 22% (TF1) and 71% (TF3). The impact of

the biological trickling filters on the concentrations of dissolved copper

concentrations was not significant at most sites. However, at TF1 and TF5 significant

differences between dissolved copper in settled sewage and the effluent from the

biological treatment process indicate that substantial dissolution of copper occurred

(76% and 94% respectively), highlighting the unpredictable nature of this treatment

process in the removal of dissolved copper. It is possible that the rate of the

recirculation over the trickling filters, which varied considerably (Table 1), may have

changed the characteristics of the settled sewage by influencing redox potential

(dissolved oxygen concentration) and decreasing suspended solids, which could in

turn affect partitioning.

It was apparent that some of the tertiary treatment processes had the potential

to further reduce the total copper load discharged to the environment in final effluents,

although, their performance in this respect was variable. This was highlighted by the

variable performance of the BAFF processes installed at TF4 and TF6 sites (Table 4).

All tertiary processes designed to remove solids (RGF, COUF and BAFF) reduced the

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load of total copper, probably as a result of decreasing suspended solids load,

although only the BAFF at TF4 removed dissolved copper, and at TF2, the COUF

was observed to increase concentrations of dissolved copper.

Table 3 Average removal efficiencies (%) of total and dissolved copper across

conventional unit treatment processes at each site. Negative values indicate an

increase in concentration.

Site Primary treatment Biological treatment

Total Dissolved Total Dissolved

TF1 53 13 22 -76 a

TF2 60 0 52 17

TF3 59 41 a 71 16

TF4 49 -1 50 -5

TF5 54 28 a 55 -94

a

TF6 38 -7 52 -7

TF7 53 49 44 -17

ASP 59 - 94 50 a

a Statistically significant (p=0.05)

Fig. 3 – The overall removal efficiencies from crude sewage to final affluent of total

(■) and dissolved (□) copper at the eight STWs. Negative removals indicate an

increase in concentration was observed.

-60

-40

-20

0

20

40

60

80

100

TF7 TF2 TF3 TF4 TF6 ASP

TricklingFilters

Trickling Filters withTertiary Treatment

TF1 TF5

Rem

ov

al e

ffic

ien

cy f

or

cop

per

(%)

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Table 4 Average removal efficiencies (%) of total and dissolved copper across

tertiary treatment units. Negative values indicate an increase in concentration.

Site NTF BAFF RGF/COUF

Total Dissolved Total Dissolved Total Dissolved

TF2 -15 20 - - 45 -50 a

TF3 -15 -3 - - 32 -3

TF4 - - 61 52 a - -

TF6 - - 33 -2 - - a Statistically significant (p=0.05).

The overall performance of each complete STW, in terms of the removal

efficiency calculated between crude sewage and final effluent, are displayed in Figure

3. Although an attempt has been made to present the sites grouped by the treatment

processes present, there is no clear benefit displayed for the removal of copper when

tertiary processes are present. It is apparent, however, that the ASP was most effective

in removing total copper, but as crude sewage could not be sampled here, no value

could be calculated for removal of dissolved copper.

3.4. Concentrations in final effluent

The average concentrations of total and dissolved copper in the final effluents

from the STW ranged from 1.0 µg/l (dissolved) at the ASP to 15.2 µg/l (total) at TF4

(Fig. 4). As observed in crude sewage, there was a significant spatial variation in both

dissolved and total copper concentrations. However, the phase distribution in the final

effluents had markedly changed, in comparison to crude sewage, with a higher

proportion of copper being present in the dissolved phase and accounting for 26%

(TF4) up to 77% (TF5) of the total metal concentration. Additionally, the treatment

smoothed the temporal variation initially present in the crude sewages and there was

no diurnal pattern visible in the final effluent concentrations. In this set of data, the

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quality of the effluent from the ASP was noticeably superior, even when compared

with the final effluents from trickling filter works incorporating tertiary treatment

processes.

4. Discussion

At most of the sites investigated, the concentrations of copper present in the

crude sewage were in the lower range of values recently reported (Karvelas et al.,

2003; Rule et al., 2006; Olivieira et al., 2007). Industrial inputs were not significant at

the sites studied, and diurnal variations indicated domestic users may be an important

source of copper to the STWs. Leaching from copper pipes is considered to be the

primary source of copper to STWs from domestic and commercial areas (Bouley and

Edwards, 2000; Sorme and Lagerkvist, 2002; Landner and Reuther, 2004). There is,

however, evidence that inputs from plumbing are decreasing, due to phosphate dosing

of potable water, which is known to significantly reduce the leaching of copper from

plumbing into the water supply (Edwards et al., 2002; Goh et al., 2008) and it is

known that phosphate dosing of potable supplies in the area studied was instigated

between 1997 and 1999 (United Utilities, 2001).

Fig. 4 - Total (■) and dissolved (□) copper concentrations (µg/l) in final effluents.

0

2

4

6

8

10

12

14

16

18

Cop

per

con

centr

atio

n,µ

g/

l

TF1 TF2 TF3 TF4 TF5 TF6 TF7 ASP

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Regardless of the source, during this study copper in the influent was

predominantly found in the particulate form (70-93%) i.e. associated with solid

matter. This is in agreement with observation by other authors (Goldstone et al.,

1990a; Karvelas et al., 2003; Buzier et al., 2006), and therefore, copper was expected

to be efficiently removed during the primary sedimentation process. Moreover, the

addition of retuned liquors that typically contained less than 1% of copper in the

dissolved form further increased the ratio of total to dissolved metal. The removal

efficiencies of total copper observed in primary treatment during this study averaged

53% and were generally in the higher range of reported values (Olivier and Cosgrove,

1974; Kempton et al., 1987a; Goldstone et al., 1990a; Karvelas et al., 2003).

However, removal of dissolved copper during primary sedimentation was also

observed at three STWs. This phenomenon appears to be a consequence of the

addition of the returned liquors to the crude sewage. Retuned liquors typically contain

a large amount of suspended solids that may enhance partitioning of dissolved copper

onto the solid phase. Such behaviour has been reported previously (Goldstone et al.,

1990a; Buzier et al., 2006), although there is also evidence that the addition of

returned liquors may have the effect of increasing the concentration of dissolved

copper in the settled sewage (Brown et al., 1973). An increase in suspended solids

through the addition of returned liquors may also positively affect the removal of

copper associated with particles by increasing flocculation (Stoveland and Lester,

1980; Kempton et al., 1987b). However, variability in removal efficiencies

demonstrated that although the addition of returned liquors potentially enhanced

copper removal, site specific factors such as the nature / type of returned liquors may

have an impact on the fate of copper during primary treatment.

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The removal efficiency of total copper during biological treatment varied from

22% to 71% on sites utilising trickling filters. Although during this study, the one site

utilising the activated sludge process performed considerably better (94%) than the

trickling filters, the removal values reported for this process also vary widely, from

25% (Roberts et al., 1977) through 43% (Karvelas et al., 2003) and 61% (Goldstone et

al., 1990a) up to 79% (Lester et al., 1979). This implies that although biological

treatment processes have the potential to significantly remove copper, the ultimate

performance is highly site specific and may depend on both physico-chemical

characteristics of the sewage (Sterritt et al., 1981) and operational parameters (Sterritt

and Lester, 1981). If dissolution of copper occurs across the biological process, this is

likely to reduce the effectiveness of any tertiary treatment process which reduces the

suspended solids in reducing the final concentration of copper discharged.

5. Conclusions

There was a wide temporal variability in copper concentrations in crude

sewage, however, they tend to follow the variation in diurnal flow which strongly

suggest they are indicative of copper originating from the water supply systems.

There is a wide variation in the removal efficiencies of copper between sites,

and this is especially evident for the dissolved metal fraction. Operational parameters

such as returned liquors and recirculation over trickling filters may all have an impact

on the removal of copper.

As the majority of the copper present following biological treatment was in the

dissolved phase, optimisation of existing conventional treatment processes (primary

and biological treatment) to maximise dissolved copper removal may have a

substantial impact on the overall removal efficiency of the STW and be a more cost

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effective option than installing any tertiary process to specifically reduce the

discharge of copper.

Acknowledgements

The authors are grateful to United Utilities PLC for funding the work and for

permission to publish the results

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Table headers

Table 1 Site characteristics and operational parameters recorded during the

sampling periods.

Table 2 Total and dissolved copper concentrations (µg/l) in return flows.

Table 3 Average removal efficiencies (%) of total and dissolved copper across

conventional unit treatment processes at each site. Negative values indicate an

increase in concentration.

Table 4 Average removal efficiencies (%) of total and dissolved copper across

tertiary treatment units. Negative values indicate an increase in concentration.

Figure legends

Fig. 1. - Total (■) and dissolved (□) copper concentrations (µg/l) in crude sewage.

Data for the ASP is calculated from mass balances.

Fig. 2. - Temporal variation in total (■) and dissolved (□) copper concentrations (µg/l)

showing a diurnal pattern with flow (l/s) to full treatment (―) at TF5.

Fig. 3 – The overall removal efficiencies from crude sewage to final affluent of total

(■) and dissolved (□) copper at the eight STWs. Negative removals indicate an

increase in concentration was observed.

Fig. 4 - Total (■) and dissolved (□) copper concentrations (µg/l) in final effluents.